基于阻抗模型解析的氧化锆固体电解质组织结构演变模型

晶界对多元多晶电解质材料电导率的影响, 已成为制约高温固体电解质材料发展的瓶颈. 传统的晶界观察方法难以将高温下材料的组织结构与电导性能相对应. 鉴于此, 本文研究了部分稳定氧化锆(PSZ) 固体电解质材料的变温交流阻抗特性, 并对交流阻抗谱进行了拟合分析, 发现等效拟合电路随温度的上升而发生变化. 通过对不同等效电路模型的物理解析, 得出PSZ电解质材料显微结构在高温下的演变模型. 经进一步分析, 演绎出一种'短程有序'的'晶界桥接'组织模型, 为改善PSZ电解质材料的晶界电导提供了参考.     

Ba0.98Ce0.8Tm0.2O3-α的离子导电性及其燃料电池性能

用高温固相反应法制备了Ba_0.98Ce_0.8Tm_0.2O_3-α钙钛矿型氧化物固溶体，粉末X射线衍射表明该固溶体为单相. 用交流阻抗谱技术和气体浓差电池方法研究了样品在500～900 oC、不同气体气氛中的导电性，以及该样品为固体电解质的氢-空气燃料电池性能. 该电池能稳定地工作，在900 oC时，电池的最大功率密度为110.2 mW/cm²，高于以Ba_xCe_0.8RE_0.2O₃^- (x≤1, RE=Y, Eu, Ho)为固体电解质的氢-空气燃料电池的功率密度     

固体氧化物燃料电池体系掺杂氧化锆的理论研究：从结构到导电性

固体氧化物燃料电池是一种将化学能(如H₂和O₂)转化为电能的清洁能源系统,它具有高效、低碳以及燃料适应性广的特点. 作为燃料电池的“心脏”,电解质决定了整个电池的性能,其中掺杂氧化锆是最为典型的燃料电池电解质材料. 氧化钇稳定氧化锆在高温下具有优良的离子电导率,广泛应用在固体燃料电池中. 电解质材料的组成和使用温度对电导率的影响在实验和理论上已得到了充分研究. 复合氧化物的原子结构的表征是阐明其导电行为的关键,本文综述了氧化钇稳定氧化锆电解质的结构和导电性研究的最新理论进展,比较了研究该材料所采用的不同的理论方法及其相应结果,并总结了各种方法的优缺点. 重点介绍了利用随机表面行走-神经网络方法取得的最新成果,这些成果和实验结果相吻合. 结果表明,采用机器学习进行原子模拟为理解固体电解质中遇到的复杂物质现象提供了一种经济、高效和准确的方法.     

Sn3InSb4合金嵌Li性能的第一性原理研究

采用第一性原理超软赝势平面波方法计算了Sn₃InSb₄的嵌Li性能,得到各种嵌Li相的嵌Li形成能、理论质量比容量、体积膨胀率、能带结构、态密度和差分电荷密度等.从能量角度分析,Li在嵌入时,优先占据晶胞的四面体间隙位置,然后逐步挤出处于节点位置的Sn原子和In原子.在嵌Li过程中,材料表现出较大的体积膨胀率(11.74%-43.40%),这是导致Sn₃InSb₄作为Li离子电极材料循环性能差的重要原因.态密度计算表明,体系的导电性能首先随嵌Li量的增加而增加,当所有的间隙位置被Li填满,发生Sn的替换反应时,富Li态合金相的导电性反而下降.     

Cd0.9Zn0.1Te晶体的Cd气氛扩散热处理研究

将生长得到的Cd_0.9Zn_0.1Te晶体在Cd气氛下及不同的温度条件下进行了退火处理. 借助已建立的退火处理过程中Cd_1-xZn_xTe晶体材料电阻率及导电类型变化和扩散杂质的扩散系数之间关系的模型，结合实验数据，获得了1073K，973K和873K下Cd在Cd_0.9Zn_0.1Te晶体中的扩散系数，并估算了其激活能. 通过使用获得的扩散系数，研究了在不同温度及饱和Cd气氛下，退火时间对Cd_0.9Zn_0.1Te晶体电阻率分布及导电类型等的变化的影响.     

钼掺杂对SrCo0.8Fe0.2O3-δ的氧渗透性能和化学稳定性的影响

研究了SrCo_0.7Fe_0.2Mo_0.1O_3-δ(SCFM)材料的相组成、微观结构、热膨胀系数、氧渗透性能和化学稳定性, 其结果和文献中的SrCo_0.8Fe_0.2O_3-δ(SCF)做了对比．通过EDTA-citric混合方法成功获得了纯相SCFM材料．SCFM材料在500～1050 oC显示出比SCF材料更低的热膨胀系数(24×10^{-6相似文献}   

电子束蒸发法制备ZrO2薄膜的相变模型分析

 用电子束蒸发方法制备了纯的ZrO₂薄膜和含Y₂O₃摩尔分数为7%和13%的ZrO₂薄膜，即YSZ薄膜，通过测定薄膜的损伤阈值来验证温度诱导相变模型；并用X射线衍射（XRD）来测定ZrO₂和YSZ镀膜材料和薄膜的结构特征。结果表明：ZrO₂镀膜材料和薄膜室温下都表现为单斜相，YSZ镀膜材料和薄膜室温下都以立方相存在；YSZ薄膜的损伤阈值远高于ZrO₂薄膜的损伤阈值，这是因为添加Y₂O₃后的YSZ材料的相比较稳定，在蒸发过程中不会发生相变，而ZrO₂材料则发生相变，产生缺陷，缺陷在激光作用下成为吸收中心和初始破坏点，导致ZrO₂薄膜的损伤阈值降低。     

BaFe0.4Sn0.6O3/BaBiO3负温度系数复合热敏陶瓷阻抗分析

以BaBiO₃为导电相,BaFe_0.4Sn_0.6O₃为高阻相,采用固态反应法制备了不同BaBiO₃含量的BaFe_0.4Sn_0.6O₃/BaBiO₃负温度系数(NTC)热敏复合陶瓷.为获得在渗流阈值(即BaBiO₃含量为12 mol%)前后复合陶瓷的内部导电机理,对复合陶瓷进行了阻抗分析.分     

固体颗粒的结构演化与机械力化学效应

干法、室温振动研磨制备铝超微颗粒, 分别将研磨2 h, 4 h和8 h的铝粉, 在常温下超声水解得到白色Al(OH)₃胶体, 水解产品经干燥、研磨、焙烧后制备出多孔、片状γ -Al₂O₃纳米颗粒, 粒度分布在30---50 nm之间. 借助于X射线衍射(XRD)分析方法和透射电子显微镜(TEM), 研究固体颗粒在细化过程中的能量转换, 分析颗粒的微结构演化与机械力化学反应的关系, 确定理想的研磨时间. 研究结果表明: 固体颗粒在机械力的作用下产生大量的应变和位错缺陷, 使材料处于亚稳、高能活性状态, 易于诱发机械力化学反应, 在一定条件下晶体的表面能、应变能和层错能相互转化; 研磨2 h的铝颗粒内部, 晶格畸变和位错概率最大, 材料显示出极高的化学反应活性, 在超声波激发下, 储存在材料内部的能量被充分释放, 在较短的时间内, 水解生成Al(OH)₃纳米颗粒.     

Mn掺杂LiFePO4的第一性原理研究

采用基于密度泛函理论的第一性原理方法, 计算了不同Mn掺杂浓度LiFe_1-xMn_xPO₄ (x=0,0.25,0.50,0.75) 的电子结构. 同时采用流变相辅助高温固相碳热还原法制备了LiFe_1-xMn_xPO₄ (x= 0,0.25,0.50,0.75) 材料. 理论计算表明: LiFePO₄具有E_g = 0.725 eV的带隙宽度, 为半导体材料. 通过Fe位掺杂25%的Mn离子可最大程度地 减小材料带隙宽度、降低Fe---O键及Li---O键键能, 进而提高材料的电子电导率及锂离子扩散速率. 实验结果亦表明, 当Mn掺杂量x=0.25时, 材料具有最优的电化学性能, 其具有约为158 mAh· g^-1的放电比容量以及551 Wh· kg^-1的能量密度. 理论计算与实验结果非常符合.     

Thermal conductivity of Pb-Mg-Zr alloys and the thermal resistance of the interface between alloys and EP-823 steel in the temperature range of 300–900°C

A technique for measuring the thermal resistance of the liquid metal–structural steel interface is proposed. The results ofmeasurements of the thermal resistance of the interface between Pb-Mg-Zr alloys and EP-823 steel and the thermal conductivity of Pb-Mg-Zr alloys in the temperature range of 350–900 °C are presented.     

Nb掺杂对还原性烧结的TiO2-δ陶瓷的晶体结构及热电性能的影响

利用传统的固相反应法在还原性气氛1200 ℃下分别制备出不同Nb掺杂量的Ti_1-xNb_xO_2-δ陶瓷样品.样品的粉末X射线衍射(XRD)结果显示:Nb掺杂量x较低时样品为多相混合,当Nb掺杂量x>0.02时样品为单一的四方相金红石型结构.在室温到900 K的测试温区,测试了单相样品(x=0.02,0.03,0.04)的电导率、Seebeck系数和热导率.测试 关键词： 氧化钛陶瓷 热电性能 氧空位     

Electrical conductivity studies of mixed phthalocyanine thin films

Thin films of mixed of Copper Phthalocyanine (CuPc) and Nickel Phthalocyanine (NiPc) are deposited onto a pure glass substrate by a simultaneous thermal evaporation technique at room temperature. The material D.C. electrical conductivity of films at room temperature and also films annealed at 523 K has been investigated. The optical absorption and band gaps of the films are also measured. The results show that the electrical resistance is lower for the mixed films compared with the pure samples and also the optical band gap decreases for the mixed samples compared to the pure samples.     

Thermal conductivity of indium at high pressures and temperatures under shock compression

The results of investigations of the electrical and thermal conductivity of indium in the pressure range up to 27 GPa and at temperatures up to 1000 K are presented. In this pressure range, the electrical resistance of indium samples is measured under multishock compression. The equation of state constructed for indium is used to calculate the evolution of the thermodynamic parameters of indium in shock wave experiments; then, the dependences of the electrical resistivity and thermal conductivity coefficient on the volume and temperature are determined. It is demonstrated that, in the pressure and temperature ranges under investigation, the thermal conductivity coefficient of indium does not depend on temperature and its threefold increase is caused only by the change in the volume under compression.     

Measurement of surface resistivity/conductivity of metallic alloys in aqueous solutions by optical interferometry techniques

Optical interferometry techniques were used for the first time to measure the surface resistivity/conductivity of the pure aluminium (in seawater at room temperature), UNS No.304 stainless steel (in seawater at room temperature), and pure copper (in tap water at room temperature) without any physical contact. This was achieved by applying an electrical potential across the alloys and measuring the current density flow across the alloys, during the cyclic polarization test of the alloys in different solutions. In the mean time, optical interferometry techniques such as holographic interferometry were used in situ to measure the orthogonal surface displacement of the alloys, as a result of the applied electrical potential. In addition, a mathematical model was derived in order to correlate the ratio of the electrical potential to the current density flow (electrical potential/electronic current flow = resistance) and to the surface (orthogonal) displacement of the metallic samples. In other words, a proportionality constant (surface resistivity or conductivity = 1/surface resistivity) between the measured electrical resistance and the surface displacement (by the optical interferometry techniques) was obtained. Consequently the surface resistivity (ρ) and conductivity (σ) of the pure aluminium (in seawater at room temperature), UNS No.304 stainless steel (in seawater at room temperature), and pure copper (in tap water at room temperature) were obtained. Also, electrical resistivity values (ρ) from other source were used for comparison sake with the calculated values of this investigation. This study revealed that the measured value of the resistivity for the pure aluminium (7.7 × 10¹⁰ Ω cm in seawater at room temperature) is in good agreement with the one found in literature for the aluminium oxide, 85% Al₂O₃ (5 × 10¹⁰ Ω cm in air at temperature 30 °C). Unfortunately, there is no measured value for the resistivity of cupric oxide (CuO), cuprous oxide (Cu₂O), or even the oxide of the UNS No.304 stainless steel in literature comparing those values with the measured values in this study.     

Thermal conductivity of thermoelectric Al‐substituted ZnO thin films

ZnO:Al thin films with a low electrical resistivity were grown by magnetron sputtering on sapphire substrates. The cross‐plane thermal conductivity (κ = 4.5 ± 1.3 W/mK) at room temperature is almost one order of magnitude lower than for bulk materials. The thermoelectric figure of merit ZT at elevated temperatures was estimated from in‐plane power factor and the cross‐plane thermal conductivity at room temperature. It is expected that the thermal conductivity drops with increasing temperature and is lower in‐plane than cross‐plane. Consequently, the thin film ZT is at least three times higher than for bulk samples at intermediate temperatures. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Semiconductor-metal transition in selenium under shock compression

Phase transitions in selenium are studied by time-resolved measurements of the electrical conductivity under shock compression at a pressure of up to 32 GPa. The pressure dependence of the electrical conductivity (σ(P)) has two portions: a sharp increase at P < 21 GPa and a plateau at P > 21 GPa. The experimental data and the temperature estimates indicate that, at P < 21 GPa, selenium is in the semiconductor state. The energy gap of semiconducting selenium decreases substantially under compression. At P > 21 GPa, the electrical conductivity saturates at ～10⁴ Ω^?1 cm^?1. Such a high value of the electrical conductivity shows the effective semiconductor-metal transition taking place in shock-compressed selenium. Experiments with samples having different initial densities demonstrate the effect of temperature on the phase transition. For example, powdered selenium experiences the transition at a lower shock pressure than solid selenium. Comparison of the temperature estimates with the phase diagram of selenium shows that powdered selenium metallizes in a shock wave as a result of melting. The most plausible mechanism behind the shock-induced semiconductor-metal transition in solid selenium is melting or the transition in the solid phase. Under shock compression, the metallic phase arises without a noticeable time delay. After relief, the metallic phase persists for a time, delaying the reverse transition.     

Thermal conductivity: A review of some important developments

Some recent developments are presented which relate to the thermal conductivity of metals and its measurement. These include the influence of sample size on the electronic thermal conductivity of very pure metals, the thermal conductivity minimum of aluminium and a few other metals at sub-normal temperatures, the high-temperature thermal conductivity and increasing Lorenz function of platinum, with particular reference to the experiments of Flynn and O'Hagan (1967), the thermal conductivity of molten metals and the recently reported Lorenz functions decreasing with increase in temperature to well below the theoretical value, and the encouraging results of an investigation in progress at the Thermophysical Properties Research Center (TPRC) on direct electrical heating methods for the measurement of metallic thermal conductivities to high temperatures. Modern computer techniques avoid the restrictions and approximations introduced in the many existing methods and allow thermal conductivity to be accurately evaluated from the observed temperature profile. This method has the additional advantage that many other properties can be obtained to high temperatures for the same sample and experimental conditions. The account shows that despite the amount of effort already devoted to thermal conductivity determinations, this still remains a most rewarding field requiring further accurate measurements.     

基于拉曼热测量技术的铜基复合物法兰GaN基晶体管的热阻分析

采用拉曼热测量技术结合有限元热仿真模型,分析比较新型铜/石墨复合物法兰封装与传统铜钼法兰封装的GaN器件的结温与热阻,发现前者的整体热阻比铜钼法兰器件的整体热阻低18.7%,器件内部各层材料的温度分布显示铜/石墨复合物法兰在器件中的热阻占比相比铜钼法兰在器件中的热阻占比低13%,这证明使用高热导率铜/石墨复合物法兰封装提高GaN器件热扩散性能的有效性.通过对两种GaN器件热阻占比的测量与分析,发现除了封装法兰以外,热阻占比最高的是GaN外延与衬底材料之间的界面热阻,降低界面热阻是进一步提高器件热性能的关键.同时,详细阐述了使用拉曼光热技术测量GaN器件结温和热阻的原理和过程,展示了拉曼光热技术作为一种GaN器件热特性表征方法的有效性.     

Heat capacity anomaly in UO2 in the vicinity of 1300 K: an improved description based on high resolution X-ray and neutron powder diffraction studies

X-ray and neutron powder diffraction studies of UO₂ were performed under controlled oxygen partial pressure between room temperature and 1673 K. More than 40 neutron diffraction patterns were recorded. The thermal expansion coefficient of UO₂ and the temperature dependence of Debye-Waller factors for oxygen and uranium atoms were determined. The dependence of Debye-Waller factors as a function of temperature is linear and the thermal expansion coefficient follows the classical Debye regime within the temperature range 300-1000 K. Above 1200 K, a departure from this quasi-harmonic behavior is clearly observed. Both an abnormal increase of the thermal expansion and of the oxygen sublattice disorder are evidenced. The departure of the lattice parameter from a linear thermal variation is found to be thermally activated with an effective activation energy close to 1 eV, very similar to the activation energy already found for the electrical conductivity. This new result suggests that polarons may affect the mean lattice parameter. A new thermodynamic model is then proposed to explain the heat capacity thermal variation by only three contributions: harmonic phonons, thermal expansion and polarons.